The document summarizes research on the chemistry of transactinide elements, which are located at the bottom of the periodic table. Key findings include: 1) Experiments have found trends in chemical properties that generally follow the periodic table, such as group membership, but properties can vary more than for lighter elements due to relativistic effects. 2) Research involves innovative experimental setups due to the extremely low production rates and short half-lives of transactinide elements. 3) While the periodic table is generally useful, the chemistry of transactinide elements exhibits subtleties that challenge predictions and require additional experiments to fully understand.

1. The Chemistry of the
Transactinide Elements
Matthew MacLennan
CHEM 540C
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2. Rf Db Sg Bh Hs Mt Ds Rg
2

3. Nuclear Effects
• Protons,
neutronsmagic
numbers
• 2, 8, 20, 28, 50, 82
• Island of stability
• Magic numbers are
not permanent!
• Spin-orbit coupling of
neutrons and protons
Warner, D. Nature 2004, 430, 517-519.
Schiffer, J.P.; Freeman, S.J.; Caggiano, J.A.; Deibel, C.; Heinz, A.; Jiang, C.-L.; Lewis, R.; Parikh, A.; Parker, P.D.;
Rehm, K.E.; Sinha, S.; Thomas, J.S. Phys. Rev. Lett. 2004, 92(16), 162501-1.
3

4. Electronic Effects
• Relativistic effects –
orbital
contraction/expansion
• Spin-orbit coupling
Schädel, M. Angew. Chem. Int. Ed. 2006, 45, 368-401. 4

5. Architecture of Periodic Table
Ds Rg
5

6. Preamble – “As Big as a Barn”
• Low production rates
• Barn = 10-24
cm2
; shed = 10-24
b
Schädel, M. J. Nucl. Radiochem. Sci. 2002, 3(1), 113-120. 6

7. Preamble Continued
• Need harsh conditions (acids)
• Detectable decay (i.e. not SF); usually α
7

8. Group 4
4
261
Rf78 s
8

9. Group 4
• MX4, MX6
2-
, MX7
3-
• Liquid-phase experiments confirm
Haba, H. et al. J. Am. Chem. Soc. 2004, 126, 5219-5224. 9

10. Group 4
• Test with pseudo-homologue Th, Pu
• 8M HNO3
• Chloride complexation Rf>Zr>Hf
Haba, H. et al. J. Nucl. Radiochem. Sci. 2002, 3(1), 143-146. 10

11. Group 5
5
?
262
Db34 s
11

12. Group 5
• Adsorption onto glass surfaces (KCl,
HNO3) (Group 4 = no sorption)
Hoffman, D.C.; Lee, D.M. J. Chem. Educ. 1999, 76(3), 331-347. 12

13. Group 5
• Liquid-liquid extractions of Db, Ta, Nb, Pa in
TiOA, HCl/0.03 M HF
• Ta in organic phase
• Db eluting
between Nb, Pa
Schädel, M.; Angew. Chem. Intl. Ed. 2006, 45, 368-401. 13

14. Group 6
VI
?
?
X
255,256
Sg7-20 s
14

15. Group 6
• Group 6 forms neutral or anionic
oxides, oxyhalides
• HNO3/HF[MO3F]-
, [MO2F3]-
, MO2F2
• Pseudo-homologue U UO2
2+
Schädel, M.; J. Alloys Compd. 1998, 271-273, 312-315. 15

16. Group 6
• Volatility MoO2Cl2>WO2Cl2≈SgO2Cl2
• Sg may be least volatile element yet
Türler, A. et al. Angew. Chem. Int. Ed. 1999, 38, 2212-2213. 16

17. Group 7
VII
?
?
X
X
267
Bh17 s
17

18. Group 7
• DFT calculationsMO3Cl most stable
• Volatility: TcO3Cl>ReO3Cl>BhO3Cl
Eichler, R. et al. Nature, 2000, 407, 63-65. 18

19. Group 8
VIII
?
?
X
X
269
Hs10 s
19

20. Group 8
Düllmann, Ch.E. et al. Czech. J. Phys., 2003, 53, A291-A298.
• Volatile tetroxides
• 2NaOH+HsO4Na2[HsO4(OH)2]
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21. Group 9, 10, 11
IX X XI
?
?
X
X
Half-lives0.1 s
21

22. Group 12
XII
?
?
X
X
? ? ?
283
1123.8 s
22

23. Group 12
Eichler, R. et al. Nature, 2007, 447, 72-75.
• Covalent bond with Au
• Relativistic effects?
Eichler, R. et al. Angew. Chem. Int. Ed. 2008, 47, 3262-3266. 23

24. “It’s Just a Phase You’re Going
Through…”
• 112 is more volatile than Hg!
• Gaseous metal?
Eichler, R. et al. Angew. Chem. Int. Ed. 2008, 47, 3262-3266. 24

25. MX4 MO2X2
MOX4
MO3X MO4MX5
Some More Trends
?
?
X
X
? ? ? ?
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26. Concluding Remarks
• Periodic table generally good tool
• Lacking for subtle properties
• Innovative experimental set-ups
• Qualitativemore experiments to perform
• 109-114
Nuclear Chemist when asked
to provide a straight answer…
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27. Thank you so much!
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